CN103801298A - Hydrothermal rapid synthesis method of graphene load nickel nanoparticle composite material - Google Patents
Hydrothermal rapid synthesis method of graphene load nickel nanoparticle composite material Download PDFInfo
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Abstract
The invention discloses a hydrothermal rapid synthesis method of a graphene load nickel nanoparticle composite material. The method comprises the following steps: weighing graphene oxide and nickel salt, and putting the weighed graphene oxide and nickel salt into a solvent; evenly mixing in an ultrasonic way, feeding alkali liquor and hydrazine hydrate into the mixture, and evenly mixing in an ultrasonic way again; heating for reaction; after the reaction, carrying out centrifugal separation, washing and collecting the product to obtain the graphene load nickel nanoparticle composite material. The hydrothermal rapid synthesis method is simple in technology and general in preparation conditions; the product is stable in morphology and high in purity; the product is convenient and simple to treat; therefore, the hydrothermal rapid synthesis method is suitable for medium-scale industrial production.
Description
Technical field
The invention belongs to material technology field, relate in particular to a kind of quick synthetic method of hydro-thermal of graphene-supported nickel nano particle composite.
Background technology
Nanoscale science and technology be produce late 1980s one just in the new technology of fast development.So-called nanometer technology refers to the unit with some molecules or atomic building---nanoparticle, the science and technology of manufactured materials or microdevice.Nanoparticle refers to metal or the semi-conductive fine particle of size between 1～100nm.The special construction level that nanoparticle has, give its much special character and function, nano particle has large specific area, surface atom number, surface energy and surface tension, decline with particle diameter sharply increases, skin effect, small-size effect, quantum size effect, macro quanta tunnel effect and Dielectric confinement effect etc. cause thermal and magnetic, light, sensitivity characteristic and the surface stability etc. of nano particle to be different from conventional particle, and this just makes it be with a wide range of applications.
Inorganic metal nano particle is evenly spread to graphene nanometer sheet surface and make graphene-based inorganic metal nano composite material, can not only account for the dual-use function character of tool Graphene and inorganic metal nano particle, and may produce some novel cooperative effects.Because inorganic metal nano particle itself has the performance of many excellences and application widely, the compound range of application that can further improve the performance of material, greatly widen inorganic metal nano particle and Graphene of they and Graphene.Because the size of nano material and pattern directly affect the physics and chemistry character of material, so be the research of engineering of tightening control in important trend aspect nano material preparation science and technical research, comprise the control of particle size, pattern, surface state and micro-structural.Again because nano metal has a wide range of applications in every field, so explore the control synthetic method of simple, effective Graphene metal nanometer composite material, there is important theory and realistic meaning for research and the application of graphene inorganic nano metal composite.
At present, the research of graphene-supported Ni nano composition mainly contains in-situ synthesis and solution mixing method.Metal nanoparticle is grapheme modified, and this not only can overcome Van der Waals force huge between graphene layer, prevents the reunion of graphene film, and the peculiar property of single-layer graphene is retained.Meanwhile, its many Performance Ratio metals of the composite obtaining itself are more superior,, there is important using value in fields such as catalysis, ceramic chemical industry and batteries.
Summary of the invention
The object of this invention is to provide a kind of quick synthetic method of hydro-thermal of graphene-supported nickel nano particle composite.
To achieve these goals, technical scheme of the present invention is as follows:
The invention provides a kind of quick synthetic method of hydro-thermal of graphene-supported nickel nano particle composite, comprise the following steps: take graphene oxide and nickel salt is put into solvent, after ultrasonic mixing, add alkali lye and hydrazine hydrate, ultrasonic mixing again, heating is reacted, and carries out centrifugation, washing collection product obtains graphene-supported nickel nano particle composite after react.
The mass ratio of described nickel salt and graphene oxide is 7:1～22:1.
Described nickel salt is NiCl
26H
2o, concentration range is 0.01～0.03mol/L.
Described solvent is ethylene glycol.
The concentration range of described alkali lye is 0.05～0.5mol/L.
The mass ratio of described hydrazine hydrate and graphene oxide is 40:1～120:1.
180 ℃ of the temperature that described heating is reacted, the time is 14～24h.
Described washing is by deionized water and ethanol washed product respectively.
The preparation of described graphene oxide comprises the following steps:
In natural flake graphite and sodium nitrate, add the concentrated sulfuric acid, in ice-water bath, be uniformly mixed, add while stirring potassium permanganate, control temperature and continue stirring reaction, then heat up and stir, add after deionized water in batches, then add hydrogen peroxide, continue stirring reaction, while hot the dry graphene oxide that obtains after suction filtration, washing, centrifugation.
The mass ratio of described natural flake graphite and sodium nitrate is 1:1～3:1.
The mass ratio of described natural flake graphite and the concentrated sulfuric acid is 1:40～1:50.
The mass ratio of described natural flake graphite and potassium permanganate is 1:2～1:5.
The mass ratio of described natural flake graphite and hydrogen peroxide is 1:5～1:10.
Described control temperature is <10 ℃, continues to stir 1～3h.
The temperature that described intensification is stirred is 35 ℃, and mixing time is 2～3h.
Described deionized water addition is 50mL.
Describedly continue stirring reaction 1～3h after adding hydrogen peroxide.
Described washing is carried out centrifuge washing with the salt solution of 100mL5% and the deionized water of 50 ℃ successively, to filtrate pH value be 7.
Described being dried is dry 10h in 60 ℃ of vacuum drying chambers.
Owing to adopting such scheme, the present invention has following beneficial effect:
1, the present invention has realized and has utilized the presoma that common nickel salt and cheap graphite are reduction reaction, has synthesized first graphene-supported Ni nano composition by a stage reduction method.
2, method of the present invention has very high control to the particle size of product.
3, the present invention adopts simple inorganic salts as reactant, has very strong versatility.
4, the product that prepared by the present invention has good p-nitrophenol degraded catalytic performance, can be used as high performance catalyst, has comparatively vast potential for future development and application space.
5, technique of the present invention is simple, and preparation condition is general, and product stable appearance, purity are high, and product processes convenient succinctly, is suitable for medium-scale industrial production.
6, method of the present invention has mild condition, homogeneous heating, efficient energy-saving, is easy to the features such as control.
Accompanying drawing explanation
Fig. 1 is the SEM photo of the product that obtains under the multiple of 200nm in embodiment 1.
Fig. 2 is the TEM photo of the product that obtains under the multiple of 20nm in embodiment 1.
Fig. 3 is the electronic diffraction collection of illustrative plates of embodiment 1 products therefrom.
Fig. 4 is the XRD collection of illustrative plates of embodiment 1 products therefrom.
Fig. 5 is the XPS collection of illustrative plates of embodiment 1 products therefrom.
Fig. 6 is the XPS collection of illustrative plates of embodiment 1 products therefrom.
Fig. 7 is the XPS collection of illustrative plates of embodiment 1 products therefrom.
Fig. 8 is the SEM photo of the product that obtains under the multiple of 200nm in embodiment 2.
Fig. 9 is the SEM photo of the product that obtains under the multiple of 200nm in embodiment 3.
The specific embodiment
Below in conjunction with accompanying drawing illustrated embodiment, the present invention is further detailed explanation.
Embodiment 1
1) the synthetic graphene oxide of Hummers method
The first step, takes 1g natural flake graphite and 0.5g sodium nitrate (mass ratio is 2:1), is added in 250mL tri-neck round-bottomed flasks, more slowly adds the 20-30ml concentrated sulfuric acid.The course of reaction of system mechanical agitation in ice-water bath.
Second step slowly adds 2-5g potassium permanganate in whipping process, adds speed by regulation and control, and reaction temperature is controlled in 10 ℃.After adding, then continue low temperature and stir 1h.
The 3rd step, changes above-mentioned ice-water bath into oil bath heating, and temperature is controlled at 35 ℃, and continues to stir 2～3h.
The 4th step, slowly adds 50mL deionized water several times, for dilution.
The 5th step, stirs after 0.5h, adds the deionized water of 75mL50 ℃, and adds 30% hydrogen peroxide of 5～10mL, and now product can become rapidly glassy yellow, continues to stir 1h.
The 6th step, by this bright yellow solution suction filtration while hot, and carries out centrifuge washing with the salt solution of 100mL5% and the deionized water of 50 ℃ successively, approaches 7 to filtrate pH value.
The 7th step, centrifugal product under 3000rpm, collects upper strata centrifugate, in 60 ℃ of vacuum drying chambers, dries 10h, and products therefrom is graphene oxide.
2) graphene-supported Ni nano composition is synthetic
The first step, accurately prepares 0.2mol/L sodium hydroxide solution 50ml stand-by.
Second step, measures the ethylene glycol of 45ml in the beaker of 250ml, then accurately takes the graphene oxide powder that 15mg prepares, 213.3mgNiCl
26H
2o puts into ethylene glycol (nickel salt concentration is 0.02mol/L), seals beaker mouth with sealed membrane.Beaker is put into Ultrasound Instrument ultrasonic 8 hours.
The 3rd step, is transferred to the mixed solution after ultrasonic in 100ml inner liner of reaction kettle, accurately adds 1ml0.2mol/L sodium hydroxide solution, and then 2ml hydrazine hydrate mixes ultrasonic mixed solution, puts into reactor, heats 18h at 180 ℃.
The 4th step, centrifugation black precipitate goes out precipitation with the rotating speed centrifugation of 3000rpm, with deionized water and ethanol washing, discards centrifugate; Until centrifugate achromaticity and clarification is collected required product.The product newly making is dissolved in 5ml ethanol, and sealing is stored in sample cell.
After the composite obtaining characterizes by XPS, prove to contain Ni, C, O element in composite, and prove that by XRD Ni is elemental nickel but not nickel oxide.
Fig. 1 is the SEM photo of the product that obtains under the multiple of 200nm in embodiment 1; Fig. 2 is the TEM photo of the product that obtains under the multiple of 20nm in embodiment 1; Fig. 3 is the electronic diffraction collection of illustrative plates of embodiment 1 products therefrom; Electronic diffraction ring of light photo shows the existence of Graphene; Fig. 4 is the XRD collection of illustrative plates of embodiment 1 products therefrom, illustrates that the Ni element in compound is to exist with the Ni of zero-valent state rather than the form of oxide.Fig. 5 is the XPS collection of illustrative plates of embodiment 1 products therefrom.Fig. 6 is the XPS collection of illustrative plates of embodiment 1 products therefrom.Fig. 7 is the XPS collection of illustrative plates of embodiment 1 products therefrom.In XPS collection of illustrative plates, occurred C, the element peak of Ni, has shown the existence of these two kinds of elements.
1) the synthetic graphene oxide of Hummers method
The first step, takes 1g natural flake graphite and 0.3333g sodium nitrate, is added in 250mL tri-neck round-bottomed flasks, more slowly adds the 20-30ml concentrated sulfuric acid.The course of reaction of system mechanical agitation in ice-water bath.
Second step slowly adds 2-5g potassium permanganate in whipping process, adds speed by regulation and control, and reaction temperature is controlled in 10 ℃.After adding, then continue low temperature and stir 1h.
The 3rd step, changes above-mentioned ice-water bath into oil bath heating, and temperature is controlled at 35 ℃, and continues to stir 2～3h.
The 4th step, slowly adds 50mL deionized water several times, for dilution.
The 5th step, stirs after 0.5h, adds the deionized water of 75mL50 ℃, and adds 30% hydrogen peroxide of 5～10mL, and now product can become rapidly glassy yellow, continues to stir 1h.
The 6th step, by this bright yellow solution suction filtration while hot, and carries out centrifuge washing with the salt solution of 100mL5% and the deionized water of 50 ℃ successively, approaches 7 to filtrate pH value.
The 7th step, centrifugal product under 3000rpm, collects upper strata centrifugate, in 60 ℃ of vacuum drying chambers, dries 10h, and products therefrom is graphene oxide.
2) graphene-supported Ni nano composition is synthetic
The first step, accurately prepares 0.05mol/L sodium hydroxide solution 50ml stand-by.
Second step, measures the ethylene glycol of 45ml in the beaker of 250ml, then accurately takes the graphene oxide powder that 15mg prepares, 106.7mgNiCl
26H
2o puts into ethylene glycol (nickel salt concentration is 0.01mol/L), seals beaker mouth with sealed membrane.Beaker is put into Ultrasound Instrument ultrasonic 8 hours.
The 3rd step, is transferred to the mixed solution after ultrasonic in 100ml inner liner of reaction kettle, accurately adds 1ml0.05mol/L sodium hydroxide solution, and then 2ml hydrazine hydrate mixes ultrasonic mixed solution, puts into reactor, heats 15h at 180 ℃.
The 4th step, centrifugation black precipitate goes out precipitation with the rotating speed centrifugation of 3000rpm, with deionized water and ethanol washing, discards centrifugate; Until centrifugate achromaticity and clarification is collected required product.The product newly making is dissolved in 5ml ethanol, and sealing is stored in sample cell.Fig. 8 is the SEM figure of products therefrom in embodiment 2, shows in the time that the heat time is less than 18h, and nickel nano particle is grown immature on Graphene surface.
Embodiment 3
1) the synthetic graphene oxide of Hummers method
The first step, takes 1g natural flake graphite and 1g sodium nitrate, is added in 250mL tri-neck round-bottomed flasks, more slowly adds the 20-30mL concentrated sulfuric acid.The course of reaction of system mechanical agitation in ice-water bath.
Second step slowly adds 2-5g potassium permanganate in whipping process, adds speed by regulation and control, and reaction temperature is controlled in 10 ℃.After adding, then continue low temperature and stir 1h.
The 3rd step, changes above-mentioned ice-water bath into oil bath heating, and temperature is controlled at 35 ℃, and continues to stir 2～3h.
The 4th step, slowly adds 50mL deionized water several times, for dilution.
The 5th step, stirs after 0.5h, adds the deionized water of 75mL50 ℃, and adds 30% hydrogen peroxide of 5～10mL, and now product can become rapidly glassy yellow, continues to stir 1h.
The 6th step, by this bright yellow solution suction filtration while hot, and carries out centrifuge washing with the salt solution of 100mL5% and the deionized water of 50 ℃ successively, approaches 7 to filtrate pH value.
The 7th step, centrifugal product under 3000rpm, collects upper strata centrifugate, in 60 ℃ of vacuum drying chambers, dries 10h, and products therefrom is graphene oxide.
2) graphene-supported Ni nano composition is synthetic
The first step, accurately prepares 0.5mol/L sodium hydroxide solution 50ml stand-by.
Second step, measures the ethylene glycol of 45ml in the beaker of 250ml, then accurately takes the graphene oxide powder that 15mg prepares, 319.9mgNiCl
26H
2o puts into ethylene glycol (nickel salt concentration is 0.03mol/L), seals beaker mouth with sealed membrane.Beaker is put into Ultrasound Instrument ultrasonic 8 hours.
The 3rd step, is transferred to the mixed solution after ultrasonic in 100ml inner liner of reaction kettle, accurately adds 1ml0.5mol/L sodium hydroxide solution, and then 2ml hydrazine hydrate mixes ultrasonic mixed solution, puts into reactor, heats 22h at 180 ℃.
The 4th step, centrifugation black precipitate goes out precipitation with the rotating speed centrifugation of 3000rpm, with deionized water and ethanol washing, discards centrifugate; Until centrifugate achromaticity and clarification is collected required product.The product newly making is dissolved in 5ml ethanol, and sealing is stored in sample cell.
Fig. 9 is the SEM figure of products therefrom in embodiment 3, and while showing that the heat time is greater than 18h, nickel nano particle starts to reunite on Graphene surface.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. the quick synthetic method of the hydro-thermal of a graphene-supported nickel nano particle composite, it is characterized in that: comprise the following steps: take graphene oxide and nickel salt is put into solvent, after ultrasonic mixing, add alkali lye and hydrazine hydrate, ultrasonic mixing again, heating is reacted, and carries out centrifugation, washing collection product obtains graphene-supported nickel nano particle composite after react.
2. the quick synthetic method of the hydro-thermal of graphene-supported nickel nano particle composite according to claim 1, is characterized in that: the mass ratio of described nickel salt and graphene oxide is 7:1～22:1;
Or described nickel salt is NiCl
26H
2o, concentration range is 0.01～0.03mol/L.
3. the quick synthetic method of the hydro-thermal of graphene-supported nickel nano particle composite according to claim 1, is characterized in that: described solvent is ethylene glycol;
Or the concentration range of described alkali lye is 0.05～0.5mol/L.
4. the quick synthetic method of the hydro-thermal of graphene-supported nickel nano particle composite according to claim 1, is characterized in that: the mass ratio of described hydrazine hydrate and graphene oxide is 40:1～120:1;
Or 180 ℃ of described heating temperature of reacting, the time is 14～24h;
Or described washing is by deionized water and ethanol washed product respectively.
5. the quick synthetic method of the hydro-thermal of graphene-supported nickel nano particle composite according to claim 1, it is characterized in that: the preparation of described graphene oxide comprises the following steps: in natural flake graphite and sodium nitrate, add the concentrated sulfuric acid, in ice-water bath, be uniformly mixed, add while stirring potassium permanganate, control temperature and continue stirring reaction, then heat up and stir, add in batches after deionized water, add again hydrogen peroxide, continue stirring reaction, while hot the dry graphene oxide that obtains after suction filtration, washing, centrifugation.
6. the quick synthetic method of the hydro-thermal of graphene-supported nickel nano particle composite according to claim 5, is characterized in that: the mass ratio of described natural flake graphite and sodium nitrate is 1:1～3:1;
Or the mass ratio of described natural flake graphite and the concentrated sulfuric acid is 1:40～1:50;
Or the mass ratio of described natural flake graphite and potassium permanganate is 1:2～1:5;
Or the mass ratio of described natural flake graphite and hydrogen peroxide is 1:5～1:10.
7. the quick synthetic method of the hydro-thermal of graphene-supported nickel nano particle composite according to claim 5, is characterized in that: described control temperature is <10 ℃, continues to stir 1～3h;
Or the temperature that described intensification is stirred is 35 ℃, mixing time is 2～3h;
Or described deionized water addition is 50mL.
8. the quick synthetic method of the hydro-thermal of graphene-supported nickel nano particle composite according to claim 5, is characterized in that: described in continue stirring reaction 1～3h after adding hydrogen peroxide.
9. the quick synthetic method of the hydro-thermal of graphene-supported nickel nano particle composite according to claim 5, is characterized in that: described washing is carried out centrifuge washing with the salt solution of 100mL5% and the deionized water of 50 ℃ successively, to filtrate pH value be 7.
10. the quick synthetic method of the hydro-thermal of graphene-supported nickel nano particle composite according to claim 5, is characterized in that: described being dried is dry 10h in 60 ℃ of vacuum drying chambers.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106486291A (en) * | 2016-09-21 | 2017-03-08 | 浙江大学 | A kind of NiO/rGO composite nano materials and preparation method thereof |
| CN106824203A (en) * | 2017-02-22 | 2017-06-13 | 盐城工学院 | A kind of graphene-supported nickel nano particle composite and preparation method thereof |
| CN106893107A (en) * | 2015-12-17 | 2017-06-27 | 李新勇 | The preparation method of Graphene section bar |
| CN107808779A (en) * | 2016-09-08 | 2018-03-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | CNT/three-dimensional graphene composite material, its preparation method and application |
| CN108202146A (en) * | 2017-12-29 | 2018-06-26 | 华中科技大学 | A kind of three-dimensional porous graphene package nano zero-valence carbon/carbon-copper composite material and preparation method |
| CN108642499A (en) * | 2018-05-18 | 2018-10-12 | 赵建平 | A kind of preparation method of rust remover |
| CN108655412A (en) * | 2018-04-20 | 2018-10-16 | 西安理工大学 | A kind of preparation method of load nickel particles graphene powder |
| CN110015746A (en) * | 2019-05-13 | 2019-07-16 | 上海大学 | A kind of preparation method and application of graphene multi-element metal composite material |
| CN112973693A (en) * | 2021-03-23 | 2021-06-18 | 北京师范大学珠海校区 | Microfiber composite nano metal catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942743A (en) * | 2012-09-26 | 2013-02-27 | 北京化工大学 | Simple preparation method of graphene sheet nano composite material |
| WO2013173053A1 (en) * | 2012-05-18 | 2013-11-21 | Inhwan Do | Process of dry milling particulate materials |
-
2014
- 2014-01-26 CN CN201410038344.1A patent/CN103801298A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013173053A1 (en) * | 2012-05-18 | 2013-11-21 | Inhwan Do | Process of dry milling particulate materials |
| CN102942743A (en) * | 2012-09-26 | 2013-02-27 | 北京化工大学 | Simple preparation method of graphene sheet nano composite material |
Non-Patent Citations (1)
| Title |
|---|
| NA LI等: "A facile one-step method to produce Ni/graphene nanocomposites and their application to the thermal decomposition of ammonium perchlorate", 《CRYSTENGCOMM》 * |
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| CN106893107B (en) * | 2015-12-17 | 2020-04-21 | 李新勇 | Preparation method of graphene profile |
| CN107808779A (en) * | 2016-09-08 | 2018-03-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | CNT/three-dimensional graphene composite material, its preparation method and application |
| CN107808779B (en) * | 2016-09-08 | 2019-10-18 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube/three-dimensional graphene composite material, preparation method and application |
| CN106486291A (en) * | 2016-09-21 | 2017-03-08 | 浙江大学 | A kind of NiO/rGO composite nano materials and preparation method thereof |
| CN106824203A (en) * | 2017-02-22 | 2017-06-13 | 盐城工学院 | A kind of graphene-supported nickel nano particle composite and preparation method thereof |
| CN108202146A (en) * | 2017-12-29 | 2018-06-26 | 华中科技大学 | A kind of three-dimensional porous graphene package nano zero-valence carbon/carbon-copper composite material and preparation method |
| CN108655412A (en) * | 2018-04-20 | 2018-10-16 | 西安理工大学 | A kind of preparation method of load nickel particles graphene powder |
| CN108642499A (en) * | 2018-05-18 | 2018-10-12 | 赵建平 | A kind of preparation method of rust remover |
| CN110015746A (en) * | 2019-05-13 | 2019-07-16 | 上海大学 | A kind of preparation method and application of graphene multi-element metal composite material |
| CN112973693A (en) * | 2021-03-23 | 2021-06-18 | 北京师范大学珠海校区 | Microfiber composite nano metal catalyst and preparation method and application thereof |
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Application publication date: 20140521 |